Biosynthesis of Energetic Ingredientsproceedings.ndia.org/JSEM2006/Wednesday/Cramer.pdf · 2019-12-02 · Biosynthesis Of Energetic Ingredients Objective – Green Chemistry Microbial

Biosynthesis of Energetic Ingredients

JSEM Annual Conference

March 20-23, 2006

Randall J. Cramer, Ph.D.

Indian Head Division Naval Surface Warfare Center

Phone: (301) 744-2578

Fax: (301) 744-4843

[email protected]

Green Energetic Materials

19th Century 20 Century 21 Century

Ordnance Technology

Energetic Ingredients

Environmental

Impact

Mercury FulminateLead AzideTNTNitrocelluloseNitroglycerine

Gun ammunitionProjectilesExplosives

Toxic IngredientsPolluting Reactions Batch ProcessBenzene/Chloroform Volatile EmissionsHazardous Waste

RDXHMXCL-20HMX/NGAP/Al

Gun Systems

Fast Burning PropellantsHigh Impulse PropellantsPlastic Bonded Explosives Strategic & Tactical Missiles

Laser Ignition

Continuous ProcessingLess Toxic PropellantsLead Free PropellantsEnvironmental Cost Modeling

Energetic NanomaterialsAP ReplacementsClean Combustion CompoundsReclaimed Materials

Army Future Combat SystemNavy DDXAdvanced Gun SystemsUrban Combat Munitions

“Green Chemistry”

Renewable ResourcesAqueous SolventsClean Manufacturing Process

Classical Organic Chemistry Reduced Emissions/ Nanotechnology

& New Materials

Century 20th 21st

Mercury FulminateLead AzideTNTNitrocelluloseNitroglycerine

Gun ammunitionProjectilesExplosives

“Early Chemistry”

Toxic IngredientsPolluting Reactions Batch ProcessBenzene/Chloroform Volatile EmissionsHazardous Waste

RDXHMXCL-20HMX/NGAP/Al

Gun SystemsHE Insensitive MunitionsFast Burning PropellantsHigh Impulse PropellantsPlastic Bonded Explosives Strategic & Tactical Missiles

“Brown Chemistry”

Laser Ignition Lower VOCsContinuous ProcessingLess Toxic PropellantsLead Free PropellantsEnvironmental Cost Modeling

Energetic NanomaterialsAP ReplacementsClean Combustion CompoundsReclaimed Materials

Army Future Combat SystemNavy DDXAdvanced Gun SystemsUrban Combat Munitions

Renewable ResourcesAqueous SolventsClean Manufacturing ProcessEliminate Toxic Ingredients

Classical Organic Chemistry

Materials Replacement & Reduced Emissions/ ReducedWaste

Biotechnology,

Biosynthesis Of Energetic Ingredients

Objective – Green Chemistry

Microbial catalyzed processes as an alternative to conventional chemical-based synthesis of energetic ingredients for explosives and propellant formulations.

Biosynthesis--Green Chemistry

• Old polluting chemistry• Toxic metals and organics• Multi-step batch synthesis• Non-renewable resources

• Bioengineered microorganisms• Nonpolluting aqueous systems• Single-step continuous• Renewable resources (C02)

Biosynthesis--Green Chemistry

Environmental Benefits of Biocatalytic Chemistry

• Safe and controllable fermentation process

• Aqueous systems and mild reaction conditions

• Waste stream reduction

• Bio-renewable starting materials, i.e., sugars

• Reaction selectivity

• No heavy metal catalysts

Biosynthesis Strategies

Uses naturally occurring enzymes-- “Light Green Chemistry”

Enzyme Catalysis

• Need to isolate and purify enzyme.

• Process is limited to one- or two-step synthesis.

• Enzyme is normally unstable, looses activity

• Non-specific reactions occur.

• Difficult to recycle.

2,3-Dimethyl-2,3-Dinitrobutane

Homeland Security and International interestfor inexpensive environmentally benign source

DMDNB

Preferred Marking Agent For Plastic Explosives

• No commercial use

• Easy to detect/long shelf life

• Noncarcinogenic

• Compatible with explosives at 0.1-1.0 %

O2N NO2

CH3

H3C C C CH3

CH3

O2N NO2

CH3

H3C C C CH3

CH3

NO2H 1 eq. NaOH5% aq. ETOH

90 oC

_ NO2Na+ I2/KINO2

CH3

CH3

CH3

H3C

NO2

DMDNB

70%yield

4 51 2

NO2H 1 eq. NaOH5% aq. ETOH

90 oC

_ NO2Na+ I2/KINO2

CH3

CH3

CH3

H3C

NO2

DMDNB

70%yield

4 51 2


Traditional Synthesis of DMDNB

• High cost: $200 per pound

• Polluting waste stream: 8-10 lb per pound of DMDNB.

N N

NNFe

CH3

H3C

H3C

CO2CO2

_ _

12 3

4

567

8

I II

IIIIV

α

β

γ

δ

N N

NNFe

CH3

H3C

H3C

CO2CO2

_ _

12 3

4

567

8

I II

IIIIV

α

β

γ

δ

• Use naturally occurring enzyme horseradish peroxidase.

• Enzyme catalyzed synthesis is cleaner than current organicchemistry halogen oxidation process.

• Optimized process for enzyme activity, concentrations, pH, and temperature.


Enzyme Catalyzed Synthesis of DMDNB

Me Me

NO2

M+

Me Me

NO2HRP / H2O2

NO2NO2

Me Me

MeMe

– •0.1 M KOAc

pH 5.0

DMDNB

RadicalCoupling

Aerobic

O2

Me Me

O

+ NO2–

Anaerobic

5 7

10

Peroxidase-Catalyzed Synthesis of DMDNB

Yield = 62%


Biosynthesis Strategies

Microbial biosynthesis— “Green Chemistry”

Gene ShufflingBiocatalyst Library

pH, temperature,

solvent, solute tolerance

Expression

Productivity

Substrate/ProductTolerance

EnantioselectivitySubstrate Selectivity

Stability

Regioselectivity

Gene Shuffling: rapid production of commercial biocatalysts

Gene ShufflingBiocatalyst Library

Engineer microorganisms to perform specific chemical transformations.

• High energy plasticizer prepared by nitration of 1,2,4-butanetriol (BT).

• BTTN is less volatile, more thermally stable, and less shock sensitive than NG.

• BTTN is used in high energy propellant and explosives compositions.

• Lead-free, solventless, extrudable BTTN/PNC propellants have been studied (funded by SERDP).

• Currently used in tactical missiles.

Butanetriol Trinitrate (BTTN)

O2NOONO2

ONO2

Hellfire missile

Chaparral Short-Range Air Defense Missile Brimstone Anti-tank Missile

BTTN Users

Javelin Anti-armor Missile

Property BTTN NGDensity 1.52 g/cc 1.596 g/ccMelting Point -27 O C 13.5 O CVapor Pressure 0.147 Pa @ 20 O 0.236 Pa @ 20O CImpact Sensitivity 58 cm (2 kg wt) 15 cm (2 kg wt)Vacuum Thermal Stability 2.33 cc/gm/40 hr 11 cc/gm/1.6 hr @ 100 O C

Butanetriol Trinitrate (BTTN) BTTN is preferred over nitroglycerine (NG)

• lower melting point

• less volatile

• more thermally stable

• less shock sensitive

Biosynthesis of Butanetriol (BT)

• Current synthetic routes to BT are not environmentally benign.

• BT is expensive ($40-$50/lb).

• There are limited US sources of BT.

• Demand is limited by cost.

• Low cost BTTN could replace more hazardous nitroglycerine (NG).

• Demand for NG is 3 million pounds per year for double base propellant.


• 2-6 tons of borate salt waste produced for every ton of BT.

H3CO2CCO2CH3

OH CH3OH

O HOOH

OH+ NaBH4 + NaB(OCH3)4

Malic acidSodium

BorohydrideBorate SaltsBT

Current synthesis route for BT.

ONR MURI John W. Frost, Department of Chemistry, Michigan State University established microbe catalyzed synthesis for BT.

Niu, W.; Mapitso, M. N.; Frost, J. W. J. Am. Chem. Soc. 2003, 125, 12998.


OHHOOH

L-1,2,4-butanetriol

HO H

O

OH

OH

OH

D-xylose

HO H

O

OH

OH

OH

L-arabinose

OHHOOH

D-1,2,4-butanetriol

OHOHHOHOOHOH

L-1,2,4-butanetriolL-1,2,4-butanetriol

HOHO H

O

OHOH

OHOH

OHOH

D-xyloseD-xylose

HOHO H

O

OHOH

OHOH

OHOH

L-arabinoseL-arabinose

OHOHHOHOOHOH

D-1,2,4-butanetriolD-1,2,4-butanetriol

Biosynthesis of Butanetriol (BT)• A molecule is chiral if it is not superimposable on its mirror image.

• Molecules with chiral carbons can have two different special configurations called enantiomers.

• Enantiomers differ only by their orientation in space (R, S).

• Essentially, there are no differences in physical properties between enantiomers, except for rotation of polarized light (optical activity).

• Racemic (50:50) mixtures of enantiomers can differ in melting point compared to the pure enantiomer and are not optically active.


• BT has a chiral carbon.

• Past use has been with racemic BT.

• New biocatalyzed routes to BT provide the R or S enantiomer.

• Nitration of stereoisomers must be certified.

• Melting points of nitrated stereoisomers must be determined.

CH 2 COH

OH

CH 2 CCH2CH2O

CH 2OHCH 2

HCH 2

C CH 2CH 2

OH

OH

OHCH 2

C CH 2CH 2

O OHCH 2 COH

OH

CH 2 CCH 2CH 2O

CH 2OHCH 2

HCH 2 COH

OH

CH 2 CCH 2CH 2CH 2CH 2O

CH 2OHCH 2

HCH 2

C CH 2CH 2

OH

OH

OHCH 2

C CH 2CH 2

O OHCH 2

C CH 2CH 2

OH

OH

OHCH 2

C CH 2CH 2

O OH

Nitration of Stereoisomers

• Both racemic and S-BT were nitrated.

• Thermal properties (Tg, TMA, DSC)of resulting products were measured.

• No significant difference were found for BTTN prepared from S-BT and racemic BT.


Nitrated Racemic BT

Nitrated S-BT

(A)

(B)

(A)

(B)


DSC Tg of Nitrated BT Samples

Nitrated BT Sample Tg (oC)Nitrated Racemic BT

(A) - 65.48(B) - 66.65

(A) - 66.04(B) - 65.95

Nitrated S-BT

DSC Tg Temperature of Nitrated BT Samples


Nitrated Racemic BT

Nitrated S-BT

(A)

(B) (A)

(B)


TMA Tg of Nitrated BT Samples

Nitrated BT Sample Tg (oC)Nitrated Racemic BT

(A) - 55.11(B) - 57.82

(A) - 58.92(B) - 58.18

Nitrated S-BT

TMA Tg of Nitrated BT Samples


199.54 o C


DSC of Nitrated Racemic BT Sample

201.19 o C


DSC of Nitrated S-BT Sample

Triaminotrinitrobenzene (TATB)

• Explosive with numerous military and DOE applications- insensitive- heat resistant (280-300 oC)- high density (1.93 g/cc)

• Required by Navy for FMU-139 fuze/booster used in Mk 80 seriesbombs.

• NAVAIR has 15,000 pound per year (pre-Operation Iraqi Freedom).

• No current US supplier due to trichlorobenzene starting materialavailability and polluting waste streams.

• Navy MANTECH funded phloroglucinol route.

OEt

OEt

EtONO2

NO2O2N

NH2

NH2

H2NNO2

NO2O2N

(C2H5O)3CH 95-100oC

NH3, MeOH -10oC

90%(93%)

97%(98%)

OH

OH

HO

phloroglucinol

OH

OH

HONO2

NO2O2N

70%(67%)

1. NaNO2, NaOH2. dilute HNO3, 5-15oC3. 70% HNO3, 50-60oC

Navy MANTECH TATB Synthesis

J. Hank, T. Highsmith, A. Sanderson, and S. Velarde.ATK Thiokol Propulsion, Brigham City, Utah 84302-0707

Phloroglucinol

Pure Cellulose

• 20 million pounds NC per year (Radford)

• 200 million pounds NC lacquer (OCONUS)

• Current source: cotton linters & wood pulp

• Pure cellulose production benefits:

- source control

- quality assurance

- improved ballisticsAcetobacter

Propylene Glycol Dinitrate (PGDN); Otto Fuel

• Torpedo Fuel Developed at Indian Head in 1960

• Satisfy Both Domestic and FMS Requirements

• Formulation Used by U.S. & 12 Allied Nations

ONO2

O2NO CH2CH CH3

ONO2ONO2

O2NO CH2CH CH3

Trimethylolethane Trinitrate (TMETN)

ONO2CH3 C CH2

CH2

CH2

ONO2ONO2

ONO2CH3 C CH2

CH2

CH2

ONO2ONO2

• Energetic plasticizer for underwater explosives andInsensitive Munitions:

- SABRE- Mk 65 Quickstrike Mine- Standard Missile

High Nitrogen Compounds

NN N

N

N

NN

N

Dimethylpyrazol tetrazine(DMPT)

NN N

N

N

NN

N

NN N

N

N

NN

N


N

N N

NH

NH2

N

N N

NH

NH2

Aminotetrazole NN N

N

N

N

NNN

N

NN

NN

H

H

H

H

BTATz

NN N

N

N

N

NH2

NH

H2N

NH

H

H

BGTz

H2N NH 2

NH 2

Guanidine

NH2NH2 H2O.NH2NH2 H2O.

NN N

N

NHNH 2

NHNH2DHT

Hydrazine hydrateNH2NH20.5

NBS

NH3

1.

2.

3.

NH2NH20.5NH2NH20.5

NBS

NH3NH3

1.

2.

3.

N N

NNNH 2N N

N N

NNNH 2

DAAT(other azotetrazenes proposed)


H2NHN NHNH 2

NH NH2+ Cl-

Triaminoguanidine chloride

O OO O H 2OH 2O

Acetylacetone(2,4-pentanedione)

+N

N N

N

N

NN

N

N

N N

N

N

NN

N


H2N NH2

NH2+ Cl- NH2NH2 .H2ONH2NH2 .H2O

Dioxane H2NHN NHNH 2

NH NH2+ Cl-

Guanidinium chlorideTriaminoguanidinium chloride

Hydrazine hydrate

1.

2.

1.

2. [Ox]


H 2 N NH 2

NH 2

H 2 N NH 2

NH 2

Guanidine $40/kg

H2NHN NHNH 2

NH NH 2

H2NHN NHNH 2

NH NH 2

Triaminoguanidine $50/kg

O OO O

Acetylacetone

N

N N

NH

NH2

N

N N

NH

NH2

Aminotetrazole $270/kg (2,4 -pentanedione )

$45/kg

CL-20

NN

NN

NNNO2O2N

NO2O2N

O2N NO2

CL-20 (Hexanitrohexaisowurtzitane)

HBIW (Hexabenzylhexaisowurtzitane)

• High energy explosive and propellant ingredient• CL-20 High cost >$1,270/kg• SERDP > $ 1 million environmental investment

Summary and Conclusions

• Using Biotechnology to replace old polluting processes in explosivesmanufacturing process.

• John Frost, MSU, has identified biosynthesis pathway to butanetriol, precursor to BTTN, a potential NG replacement.

• Stereochemistry resulting from biosynthesis does not impact BTTNthermal properties.

• A biosynthesis pathway for phloroglucinol, precursor to TATB, has beenidentified.

• Pure cellulose for nitrocellulose is next in line for future development.other targets include other polyols and high nitrogen compounds of military interest.

Biosynthesis of Energetic Ingredientsproceedings.ndia.org/JSEM2006/Wednesday/Cramer.pdf · 2019-12-02 · Biosynthesis Of Energetic Ingredients Objective – Green Chemistry Microbial

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